JP7274039B2 - Substrate processing method, semiconductor device manufacturing method, substrate processing apparatus, and program - Google Patents

Description

The present disclosure relates to a substrate processing method, a semiconductor device manufacturing method, a substrate processing apparatus, and a program.

2. Description of the Related Art As one process of manufacturing a semiconductor device, a process of forming a film on a substrate using a plurality of kinds of gases is sometimes performed (see, for example, Patent Documents 1 and 2). In this case, a process of forming a film by using a plurality of kinds of gases may be performed so as to fill the concave portions provided on the surface of the substrate.

JP 2017-34196 A JP 2013-30752 A

An object of the present disclosure is to improve the properties of a film that is formed so as to fill a concave portion provided on the surface of a substrate.

According to one aspect of the present disclosure,
(a) supplying a source gas to a substrate having recesses formed on its surface; supplying a first nitrogen- and hydrogen-containing gas to the substrate; and supplying a second nitrogen- and hydrogen-containing gas to the substrate; and supplying the containing gas at a first temperature for a predetermined number of times, at least any one of the source gas, the first nitrogen- and hydrogen-containing gas, and the second nitrogen- and hydrogen-containing gas a step of forming an oligomer containing an element on the surface of the substrate and in the recess, allowing it to grow and flow to form an oligomer-containing layer on the surface of the substrate and in the recess;
(b) performing post-treatment at a second temperature equal to or higher than the first temperature on the substrate having the oligomer-containing layer formed on the surface of the substrate and in the concave portion, thereby modifying the oligomer-containing layer formed in the recess to form a film obtained by modifying the oligomer-containing layer so as to fill the recess;
technology is provided.

According to the present disclosure, it is possible to improve the characteristics of the film formed so as to fill the concave portion provided on the surface of the substrate.

1 is a schematic configuration diagram of a vertical processing furnace of a substrate processing apparatus preferably used in each aspect of the present disclosure, and is a diagram showing a vertical cross-sectional view of a processing furnace portion; FIG. FIG. 2 is a schematic configuration diagram of a vertical processing furnace of a substrate processing apparatus suitably used in each aspect of the present disclosure, and is a diagram showing the processing furnace portion in a cross-sectional view taken along the line AA of FIG. 1; 1 is a schematic configuration diagram of a controller of a substrate processing apparatus preferably used in each aspect of the present disclosure, and is a block diagram showing a control system of the controller; FIG. FIG. 4 is a diagram showing a substrate processing sequence in the first aspect of the present disclosure; FIG. FIG. 11 shows a substrate processing sequence in the second aspect of the present disclosure; FIG. 10 is a diagram showing a substrate processing sequence in the third aspect of the present disclosure; FIG.

<First aspect of the present disclosure>
The first aspect of the present disclosure will be described below with reference to FIGS. 1 to 4. FIG.

(1) Configuration of Substrate Processing Apparatus As shown in FIG. 1, the processing furnace 202 has a heater 207 as a heating mechanism (temperature control unit). The heater 207 has a cylindrical shape and is installed vertically by being supported by a holding plate. The heater 207 also functions as an activation mechanism (excitation section) that thermally activates (excites) the gas.

A reaction tube 203 is arranged concentrically with the heater 207 inside the heater 207 . The reaction tube 203 is made of a heat-resistant material such as quartz (SiO ₂ ) or silicon carbide (SiC), and has a cylindrical shape with a closed upper end and an open lower end. A manifold 209 is arranged concentrically with the reaction tube 203 below the reaction tube 203 . The manifold 209 is made of a metal material such as stainless steel (SUS), and is formed in a cylindrical shape with open upper and lower ends. The upper end of the manifold 209 engages the lower end of the reaction tube 203 and is configured to support the reaction tube 203 . An O-ring 220a is provided between the manifold 209 and the reaction tube 203 as a sealing member. Reactor tube 203 is mounted vertically like heater 207 . A processing vessel (reaction vessel) is mainly configured by the reaction tube 203 and the manifold 209 . A processing chamber 201 is formed in the cylindrical hollow portion of the processing container. The processing chamber 201 is configured to accommodate a wafer 200 as a substrate. A wafer 200 is processed in the processing chamber 201 .

In the processing chamber 201, nozzles 249a to 249c as first to third supply units are provided so as to penetrate the side wall of the manifold 209, respectively. The nozzles 249a to 249c are also called first to third nozzles. The nozzles 249a-249c are made of a non-metallic material, such as quartz or SiC, which is a heat-resistant material. Gas supply pipes 232a to 232c are connected to the nozzles 249a to 249c, respectively. The nozzles 249a to 249c are different nozzles, and each of the nozzles 249a and 249c is provided adjacent to the nozzle 249b.

The gas supply pipes 232a to 232c are provided with mass flow controllers (MFC) 241a to 241c as flow rate controllers (flow rate control units) and valves 243a to 243c as on-off valves in this order from the upstream side of the gas flow. . A gas supply pipe 232e is connected downstream of the valve 243a of the gas supply pipe 232a. Gas supply pipes 232d and 232f are connected respectively downstream of the valve 243b of the gas supply pipe 232b. A gas supply pipe 232g is connected downstream of the valve 243c of the gas supply pipe 232c. The gas supply pipes 232d-232g are provided with MFCs 241d-241g and valves 243d-243g, respectively, in this order from the upstream side of the gas flow. The gas supply pipes 232a to 232g are made of metal material such as SUS, for example.

As shown in FIG. 2, the nozzles 249a to 249c are arranged in an annular space between the inner wall of the reaction tube 203 and the wafer 200 in a plan view, along the inner wall of the reaction tube 203 from the lower part to the upper part. They are provided so as to rise upward in the arrangement direction. In other words, the nozzles 249a to 249c are provided on the sides of the wafer arrangement area in which the wafers 200 are arranged, in a region horizontally surrounding the wafer arrangement area, along the wafer arrangement area. In a plan view, the nozzle 249b is arranged so as to face an exhaust port 231a, which will be described later, in a straight line with the center of the wafer 200 loaded into the processing chamber 201 interposed therebetween. The nozzles 249a and 249c are arranged such that a straight line L passing through the center of the nozzle 249b and the exhaust port 231a is sandwiched from both sides along the inner wall of the reaction tube 203 (periphery of the wafer 200). The straight line L is also a straight line passing through the nozzle 249 b and the center of the wafer 200 . That is, it can be said that the nozzle 249c is provided on the opposite side of the straight line L from the nozzle 249a. The nozzles 249a and 249c are arranged line-symmetrically with the straight line L as the axis of symmetry. Gas supply holes 250a to 250c for supplying gas are provided on the side surfaces of the nozzles 249a to 249c, respectively. Each of the gas supply holes 250a to 250c is open to face the exhaust port 231a in a plan view, and is capable of supplying gas toward the wafer 200. As shown in FIG. A plurality of gas supply holes 250 a to 250 c are provided from the bottom to the top of the reaction tube 203 .

From the gas supply pipe 232a, a source gas such as a silane-based gas containing silicon (Si) as a main element constituting a film formed on the surface of the wafer 200 is supplied through the MFC 241a, the valve 243a, and the nozzle 249a. and supplied into the processing chamber 201 . As the silane-based gas, a gas containing Si and halogen, that is, a halosilane-based gas can be used. Halogen includes chlorine (Cl), fluorine (F), bromine (Br), iodine (I), and the like. As the halosilane-based gas, for example, a gas containing silicon, carbon (C), and halogen, that is, an organic halosilane-based gas can be used. As the organic halosilane-based gas, for example, a gas containing Si, C, and Cl, that is, an organic chlorosilane-based gas can be used.

From the gas supply pipe 232b, as the first nitrogen (N) and hydrogen (H) containing gas, for example, an amine-based gas is supplied into the processing chamber 201 via the MFC 241b, the valve 243b, and the nozzle 249b. The amine-based gas further contains C, and the amine-based gas can also be referred to as a C-, N-, and H-containing gas.

From the gas supply pipe 232c, as the second N- and H-containing gas, for example, a hydrogen nitride-based gas is supplied into the processing chamber 201 via the MFC 241c, the valve 243c, and the nozzle 249c.

From the gas supply pipe 232d, an oxygen (O) containing gas such as O and H containing gas is supplied into the processing chamber 201 via the MFC 241d, the valve 243d, the gas supply pipe 232b and the nozzle 249b.

Inert gases are supplied into the processing chamber 201 from the gas supply pipes 232e to 232g via MFCs 241e to 241g, valves 243e to 243g, gas supply pipes 232a to 232c, and nozzles 249a to 249c, respectively. Inert gases act as purge gas, carrier gas, diluent gas, and the like.

A source gas supply system (silane-based gas supply system) is mainly composed of the gas supply pipe 232a, the MFC 241a, and the valve 243a. A first N- and H-containing gas supply system (amine-based gas supply system) is mainly composed of the gas supply pipe 232b, the MFC 241b, and the valve 243b. A second N- and H-containing gas supply system (hydrogen nitride-based gas supply system) is mainly composed of the gas supply pipe 232c, the MFC 241c, and the valve 243c. An O-containing gas supply system is mainly configured by the gas supply pipe 232d, the MFC 241d, and the valve 243d. An inert gas supply system is mainly composed of gas supply pipes 232e to 232g, MFCs 241e to 241g, and valves 243e to 243g.

Any or all of the supply systems described above may be configured as an integrated supply system 248 in which valves 243a to 243g, MFCs 241a to 241g, etc. are integrated. The integrated supply system 248 is connected to each of the gas supply pipes 232a to 232g, and supplies various gases to the gas supply pipes 232a to 232g, that is, the opening and closing operations of the valves 243a to 243g and the MFCs 241a to 241g. The flow rate adjustment operation and the like are configured to be controlled by a controller 121, which will be described later. The integrated supply system 248 is configured as an integral or divided integrated unit, and can be attached/detached to/from the gas supply pipes 232a to 232g or the like in units of integrated units. It is configured so that maintenance, replacement, expansion, etc. can be performed on an integrated unit basis.

Below the side wall of the reaction tube 203, an exhaust port 231a for exhausting the atmosphere inside the processing chamber 201 is provided. As shown in FIG. 2, the exhaust port 231a is provided at a position facing the nozzles 249a to 249c (gas supply holes 250a to 250c) across the wafer 200 in plan view. The exhaust port 231a may be provided along the upper portion of the side wall of the reaction tube 203, that is, along the wafer arrangement area. An exhaust pipe 231 is connected to the exhaust port 231a. The exhaust pipe 231 is supplied with a pressure sensor 245 as a pressure detector (pressure detector) for detecting the pressure in the processing chamber 201 and an APC (Auto Pressure Controller) valve 244 as a pressure regulator (pressure regulator). , a vacuum pump 246 as an evacuation device is connected. By opening and closing the APC valve 244 while the vacuum pump 246 is operating, the inside of the processing chamber 201 can be evacuated and stopped. By adjusting the valve opening based on the pressure information detected by the pressure sensor 245, the pressure in the processing chamber 201 can be adjusted. An exhaust system is mainly composed of the exhaust pipe 231 , the APC valve 244 and the pressure sensor 245 . A vacuum pump 246 may be considered to be included in the exhaust system.

Below the manifold 209, a seal cap 219 is provided as a furnace mouth cover capable of hermetically closing the lower end opening of the manifold 209. As shown in FIG. The seal cap 219 is made of, for example, a metal material such as SUS, and is shaped like a disc. An O-ring 220 b is provided on the upper surface of the seal cap 219 as a sealing member that contacts the lower end of the manifold 209 . Below the seal cap 219, a rotating mechanism 267 for rotating the boat 217, which will be described later, is installed. A rotating shaft 255 of the rotating mechanism 267 passes through the seal cap 219 and is connected to the boat 217 . The rotating mechanism 267 is configured to rotate the wafers 200 by rotating the boat 217 . The seal cap 219 is vertically moved up and down by a boat elevator 115 as a lifting mechanism installed outside the reaction tube 203 . The boat elevator 115 is configured as a transport device (transport mechanism) for loading and unloading (transporting) the wafer 200 into and out of the processing chamber 201 by raising and lowering the seal cap 219 .

Below the manifold 209, a shutter 219s is provided as a furnace port cover that can airtightly close the lower end opening of the manifold 209 in a state in which the seal cap 219 is lowered and the boat 217 is carried out of the processing chamber 201. The shutter 219s is made of a metal material such as SUS, and is shaped like a disc. An O-ring 220c is provided on the upper surface of the shutter 219s as a sealing member that contacts the lower end of the manifold 209. As shown in FIG. The opening/closing operation (elevating/rotating operation, etc.) of the shutter 219s is controlled by the shutter opening/closing mechanism 115s.

The boat 217 as a substrate support supports a plurality of wafers 200, for example, 25 to 200 wafers 200, in a horizontal posture, aligned vertically with their centers aligned with each other, and supported in multiple stages. It is configured to be spaced and arranged. The boat 217 is made of a heat-resistant material such as quartz or SiC. At the bottom of the boat 217, a plurality of heat insulating plates 218 made of a heat-resistant material such as quartz or SiC are supported.

A temperature sensor 263 as a temperature detector is installed in the reaction tube 203 . By adjusting the power supply to the heater 207 based on the temperature information detected by the temperature sensor 263, the temperature inside the processing chamber 201 has a desired temperature distribution. A temperature sensor 263 is provided along the inner wall of the reaction tube 203 .

As shown in FIG. 3, a controller 121, which is a control unit (control means), is configured as a computer including a CPU (Central Processing Unit) 121a, a RAM (Random Access Memory) 121b, a storage device 121c, and an I/O port 121d. It is The RAM 121b, storage device 121c, and I/O port 121d are configured to exchange data with the CPU 121a via an internal bus 121e. An input/output device 122 configured as, for example, a touch panel or the like is connected to the controller 121 .

The storage device 121c is composed of, for example, a flash memory, a HDD (Hard Disk Drive), an SSD (Solid State Drive), or the like. In the storage device 121c, a control program for controlling the operation of the substrate processing apparatus, a process recipe describing procedures and conditions for substrate processing, which will be described later, and the like are stored in a readable manner. The process recipe functions as a program in which the controller 121 executes each procedure in substrate processing, which will be described later, and is combined so as to obtain a predetermined result. Hereinafter, process recipes, control programs, and the like are collectively referred to simply as programs. A process recipe is also simply referred to as a recipe. When the term "program" is used in this specification, it may include only a single recipe, only a single control program, or both. The RAM 121b is configured as a memory area (work area) in which programs and data read by the CPU 121a are temporarily held.

The I/O port 121d includes the MFCs 241a to 241g, valves 243a to 243g, pressure sensor 245, APC valve 244, vacuum pump 246, temperature sensor 263, heater 207, rotating mechanism 267, boat elevator 115, shutter opening/closing mechanism 115s, and the like. It is connected to the.

The CPU 121a is configured to read and execute a control program from the storage device 121c, and to read recipes from the storage device 121c in response to input of operation commands from the input/output device 122 and the like. The CPU 121a adjusts the flow rate of various gases by the MFCs 241a to 241g, the opening and closing operations of the valves 243a to 243g, the opening and closing operations of the APC valve 244, and the pressure adjustment by the APC valve 244 based on the pressure sensor 245 so as to follow the content of the read recipe. operation, starting and stopping of the vacuum pump 246, temperature adjustment operation of the heater 207 based on the temperature sensor 263, rotation and rotation speed adjustment operation of the boat 217 by the rotation mechanism 267, elevation operation of the boat 217 by the boat elevator 115, shutter opening/closing mechanism 115s It is configured to control the opening/closing operation of the shutter 219s by means of.

The controller 121 can be configured by installing the above-described program stored in the external storage device 123 into a computer. The external storage device 123 includes, for example, a magnetic disk such as an HDD, an optical disk such as a CD, a magneto-optical disk such as an MO, a USB memory, a semiconductor memory such as an SSD, and the like. The storage device 121c and the external storage device 123 are configured as computer-readable recording media. Hereinafter, these are also collectively referred to simply as recording media. When the term "recording medium" is used in this specification, it may include only the storage device 121c alone, may include only the external storage device 123 alone, or may include both of them. The program may be provided to the computer using communication means such as the Internet or a dedicated line without using the external storage device 123 .

(2) Substrate Processing Process An example of a processing sequence for forming a film on the surface of a wafer 200 as a substrate as one process of manufacturing a semiconductor device using the substrate processing apparatus described above will be described mainly with reference to FIG. do. In this embodiment, an example of using a silicon substrate (silicon wafer) having concave portions such as trenches and holes formed on its surface will be described as the wafer 200 . In the following description, the controller 121 controls the operation of each component of the substrate processing apparatus.

As shown in FIG. 4, in the processing sequence of this aspect,
a step of supplying a source gas to the wafer 200 having recesses formed on the surface (source gas supply); and a step of supplying a first N- and H-containing gas to the wafer 200 (first N- and H-containing gas supply). , supplying a second N- and H-containing gas to the wafer 200 (second N- and H-containing gas supply) at a first temperature a predetermined number of times (n times, where n is an integer of 1 or more) As a result, an oligomer containing an element contained in at least one of the raw material gas, the first N- and H-containing gas, and the second N- and H-containing gas is generated and grown on the surface of the wafer 200 and in the recess. , to form an oligomer-containing layer on the surface of the wafer 200 and in the recess (oligomer-containing layer formation);
By performing post treatment (hereinafter also referred to as PT) at a second temperature equal to or higher than the first temperature on the wafer 200 having the oligomer-containing layer formed on the surface of the wafer 200 and in the concave portion, the surface of the wafer 200 is a step (PT) of modifying the oligomer-containing layer formed in and in the recess to form a film in which the oligomer-containing layer is modified so as to fill the recess;
I do.

In the processing sequence shown in FIG. 4, the supply of the source gas, the supply of the first N- and H-containing gas, and the supply of the second N- and H-containing gas are performed non-simultaneously.

In this specification, the processing sequence described above may also be indicated as follows for convenience. The same notation is used also in the following explanations of modified examples including the second and third aspects.

(source gas → first N- and H-containing gas → second N- and H-containing gas) × n → PT

When the term "wafer" is used in this specification, it may mean the wafer itself, or it may mean a laminate of a wafer and a predetermined layer or film formed on its surface. In this specification, the term "wafer surface" may mean the surface of the wafer itself or the surface of a predetermined layer formed on the wafer. In the present specification, the term "formation of a predetermined layer on a wafer" means that a predetermined layer is formed directly on the surface of the wafer itself, or a layer formed on the wafer, etc. It may mean forming a given layer on top of. The use of the term "substrate" in this specification is synonymous with the use of the term "wafer".

(wafer charge and boat load)
After the boat 217 is loaded with a plurality of wafers 200 (wafer charge), the shutter 219s is moved by the shutter opening/closing mechanism 115s to open the lower end opening of the manifold 209 (shutter open). Thereafter, as shown in FIG. 1, the boat 217 supporting the plurality of wafers 200 is lifted by the boat elevator 115 and loaded into the processing chamber 201 (boat load). In this state, the seal cap 219 seals the lower end of the manifold 209 via the O-ring 220b.

(pressure regulation and temperature regulation)
After the boat loading is finished, the inside of the processing chamber 201, that is, the space in which the wafer 200 exists is evacuated (reduced pressure) by the vacuum pump 246 so as to have a desired pressure (degree of vacuum). At this time, the pressure in the processing chamber 201 is measured by the pressure sensor 245, and the APC valve 244 is feedback-controlled based on the measured pressure information (pressure adjustment). Also, the wafer 200 in the processing chamber 201 is heated by the heater 207 so as to reach a desired processing temperature. At this time, the energization state of the heater 207 is feedback-controlled based on the temperature information detected by the temperature sensor 263 so that the inside of the processing chamber 201 has a desired temperature distribution (temperature adjustment). Also, the rotation of the wafer 200 by the rotation mechanism 267 is started. The evacuation of the processing chamber 201 and the heating and rotation of the wafer 200 continue at least until the processing of the wafer 200 is completed.

(Oligomer-containing layer formation)
After that, the following steps 1 to 3 are sequentially executed.

[Step 1]
In this step, source gas is supplied to the wafer 200 in the processing chamber 201 .

Specifically, the valve 243a is opened to allow the source gas to flow into the gas supply pipe 232a. The source gas is adjusted in flow rate by the MFC 241a, supplied into the processing chamber 201 through the nozzle 249a, and exhausted through the exhaust port 231a. At this time, the source gas is supplied to the wafer 200 (source gas supply). At this time, the valves 243e to 243g may be opened to supply the inert gas into the processing chamber 201 through the nozzles 249a to 249c, respectively.

After a predetermined time has passed, the valve 243a is closed to stop the supply of the raw material gas into the processing chamber 201 . Then, the inside of the processing chamber 201 is evacuated, and gas and the like remaining in the processing chamber 201 are removed from the inside of the processing chamber 201 . At this time, the valves 243e to 243g are opened to supply the inert gas into the processing chamber 201 through the nozzles 249a to 249c. The inert gas supplied from the nozzles 249a to 249c acts as a purge gas, thereby purging the space in which the wafer 200 exists, that is, the inside of the processing chamber 201 (purge).

Examples of source gases include C- and halogen-free silane-based gases such as monosilane (SiH ₄ , abbreviation: MS) gas and disilane (Si ₂ H ₆ , abbreviation: DS) gas, and dichlorosilane (SiH ₂ Cl ₂ , abbreviation: :DCS) gas, C-free halosilane gas such as hexachlorodisilane ( _Si2Cl6 , abbreviation: _HCDS ) gas, trimethylsilane (SiH( _CH3 ) ₃ , abbreviation: TMS) gas, dimethylsilane ( _SiH2 (CH ₃ ) ₂ , abbreviation: DMS) gas, triethylsilane (SiH(C ₂ H ₅ ) ₃ , abbreviation: TES) gas, diethylsilane (SiH ₂ (C ₂ H ₅ ) ₂ , abbreviation: DES) gas, etc. Alkylsilane-based gases, bis(trichlorosilyl)methane ((SiCl ₃ ) ₂ CH ₂ , abbreviation: BTCSM) gas, 1,2-bis(trichlorosilyl)ethane ((SiCl ₃ ) ₂ C ₂ H ₄ , abbreviation: BTCSE) gas, trimethylchlorosilane (SiCl( _CH3 ) ₃ , abbreviation: TMCS) gas, dimethyldichlorosilane ( _SiCl2 ( _CH3 ) ₂ , abbreviation: DMDCS) gas, triethylchlorosilane (SiCl (C ₂ H ₅ ) ₃ , abbreviation: TECS) gas, diethyldichlorosilane (SiCl ₂ (C ₂ H ₅ ) ₂ , abbreviation: DEDCS) gas, 1,1,2,2-tetrachloro-1,2-dimethyl Disilane ((CH ₃ ) ₂ Si ₂ Cl ₄ , abbreviation: TCDMDS) gas, 1,2-dichloro-1,1,2,2-tetramethyldisilane ((CH ₃ ) ₄ Si ₂ Cl ₂ , abbreviation: DCTMDS) gas An alkylhalosilane-based gas such as gas can be used.

As the inert gas, a rare gas such as nitrogen (N ₂ ) gas, argon (Ar) gas, helium (He) gas, neon (Ne) gas, or xenon (Xe) gas can be used. This point also applies to each step described later.

[Step 2]
In this step, a first N and H containing gas is supplied to the wafer 200 in the processing chamber 201 .

Specifically, the valve 243b is opened to allow the first N- and H-containing gas to flow into the gas supply pipe 232b. The flow rate of the first N- and H-containing gas is adjusted by the MFC 241b, supplied into the processing chamber 201 through the nozzle 249b, and exhausted through the exhaust port 231a. At this time, a first N- and H-containing gas is supplied to the wafer 200 (first N- and H-containing gas supply). At this time, the valves 243e to 243g may be opened to supply the inert gas into the processing chamber 201 through the nozzles 249a to 249c, respectively.

After a predetermined time has passed, the valve 243b is closed and the supply of the first N- and H-containing gas into the processing chamber 201 is stopped. Then, the gas remaining in the processing chamber 201 is removed from the processing chamber 201 by the same processing procedure and processing conditions as the purge in step 1 .

Examples of the first N- and H-containing gas include hydrogen nitride-based gas such as ammonia (NH ₃ ) gas, monoethylamine (C ₂ H ₅ NH ₂ , abbreviation: MEA) gas, diethylamine ((C ₂ H ₅ ) ₂ NH, abbreviation: DEA) gas, ethylamine-based gas such as triethylamine ((C ₂ H ₅ ) ₃ N, abbreviation: TEA) gas, monomethylamine (CH ₃ NH ₂ , abbreviation: MMA) gas, dimethylamine ((CH ₃ ) _2NH (abbreviation: DMA) gas, methylamine-based gas such as trimethylamine ((CH ₃ ) ₃ N, abbreviation: TMA) gas, and monomethylhydrazine ((CH ₃ )HN ₂ H ₂ , abbreviation: MMH) gas , organic hydrazine-based gases such as dimethylhydrazine ((CH ₃ ) ₂ N ₂ H ₂ , abbreviation: DMH) gas, trimethylhydrazine ((CH ₃ ) ₂ N ₂ (CH ₃ )H, abbreviation: TMH) gas, pyridine Cyclic amine-based gases such as (C ₅ H ₅ N) gas and piperazine (C ₄ H ₁₀ N ₂ ) gas can be used.

[Step 3]
In this step, a second N and H containing gas is supplied to the wafer 200 in the processing chamber 201 .

Specifically, the valve 243c is opened to allow the second N- and H-containing gas to flow into the gas supply pipe 232c. The flow rate of the second N- and H-containing gas is adjusted by the MFC 241c, supplied into the processing chamber 201 through the nozzle 249c, and exhausted through the exhaust port 231a. At this time, a second N- and H-containing gas is supplied to the wafer 200 (second N- and H-containing gas supply). At this time, the valves 243e to 243g may be opened to supply the inert gas into the processing chamber 201 through the nozzles 249a to 249c, respectively.

After a predetermined time has passed, the valve 243c is closed and the supply of the second N- and H-containing gas into the processing chamber 201 is stopped. Then, the gas remaining in the processing chamber 201 is removed from the processing chamber 201 by the same processing procedure and processing conditions as the purge in step 1 .

As the second N- and H-containing gas, for example, a hydrogen nitride-based gas such as ammonia (NH ₃ ) gas, diazene (N ₂ H ₂ ) gas, hydrazine (N ₂ H ₄ ) gas, N ₃ H ₈ gas may be used. can be done. As the second N- and H-containing gas, it is preferable to use a gas having a molecular structure different from that of the first N- and H-containing gas. However, depending on the processing conditions, it is possible to use a gas having the same molecular structure as the first N- and H-containing gas as the second N- and H-containing gas.

[Predetermined number of times]
Thereafter, a cycle of performing steps 1 to 3 described above asynchronously, that is, without synchronization, is performed a predetermined number of times (n times, where n is an integer equal to or greater than 1).

At this time, when the raw material gas exists alone, the cycle is performed a predetermined number of times under the condition (temperature) in which the physical adsorption of the raw material gas is dominant over the chemisorption of the raw material gas. Preferably, when the raw material gas exists alone, the cycle is performed a predetermined number of times under the conditions (temperature) where the physical adsorption of the raw material gas is dominant over the thermal decomposition of the raw material gas and the chemisorption of the raw material gas. . Further, preferably, the cycle is performed under conditions (temperature) in which, when the raw material gas exists alone, the raw material gas is not thermally decomposed and physical adsorption of the raw material gas is predominantly caused rather than chemisorption of the raw material gas. Repeat a predetermined number of times. Further, preferably, the cycle is performed a predetermined number of times under conditions (temperature) that make the oligomer-containing layer fluid. Further, preferably, the cycle is performed under the conditions (temperature) in which the oligomer-containing layer is caused to flow deep into the recess formed on the surface of the wafer 200, and the oligomer-containing layer fills the recess from the deep inside of the recess. Repeat a predetermined number of times.

The processing conditions for supplying the raw material gas are as follows.
Raw material gas supply flow rate: 10 to 1000 sccm
Raw material gas supply time: 1 to 300 seconds Inert gas supply flow rate (per gas supply pipe): 10 to 10000 sccm
Treatment temperature (first temperature): 0 to 150°C, preferably 10 to 100°C, more preferably 20 to 60°C
Treatment pressure: 10-6000 Pa, preferably 50-2000 Pa
are exemplified.

In this specification, the expression of a numerical range such as "0 to 150°C" means that the lower limit and the upper limit are included in the range. Therefore, for example, "0 to 150°C" means "0°C to 150°C". The same applies to other numerical ranges.

The treatment conditions for supplying the first N- and H-containing gas are as follows:
First N- and H-containing gas supply flow rate: 10 to 5000 sccm
First N- and H-containing gas supply time: 1 to 300 seconds are exemplified. Other processing conditions can be the same as the processing conditions for supplying the raw material gas.

The processing conditions for supplying the second N- and H-containing gas are as follows:
Second N- and H-containing gas supply flow rate: 10 to 5000 sccm
Second N- and H-containing gas supply time: 1 to 300 seconds are exemplified. Other processing conditions can be the same as the processing conditions for supplying the raw material gas.

By performing the raw material gas supply, the first N- and H-containing gas supply, and the second N- and H-containing gas supply under the above-described processing conditions, at least one of the raw material gas, the first N- and H-containing gas, and the second N- and H-containing gas An oligomer containing an element contained in either is generated on the surface of the wafer 200 and in the recess, allowed to grow and flow, and an oligomer-containing layer can be formed on the surface of the wafer 200 and in the recess. . The term "oligomer" refers to a polymer having a relatively low molecular weight (eg, a molecular weight of 10,000 or less) in which a relatively small amount (eg, 10 to 100) of monomers are bonded. When using an alkylhalosilane-based gas such as an alkylchlorosilane-based gas, an amine-based gas, or a hydrogen nitride-based gas as the raw material gas, the first N- and H-containing gas, and the second N- and H-containing gas, respectively, the oligomer-containing layer is , Si, Cl, and N, and substances represented by the chemical formula C _x H _2x+1 (where x is an integer of 1 to 3) such as CH ₃ and C ₂ H ₅ .

If the processing temperature is less than 0° C., the raw material gas supplied into the processing chamber 201 tends to be liquefied, and it may be difficult to supply the raw material gas in a gaseous state to the wafers 200 . . In this case, the reaction for forming the oligomer-containing layer described above may be difficult to proceed, and it may be difficult to form the oligomer-containing layer on the surface of the wafer 200 and in the recess. This problem can be solved by setting the treatment temperature to 0° C. or higher. By setting the treatment temperature to 10° C. or higher, it is possible to sufficiently solve this problem, and by setting the treatment temperature to 20° C. or higher, it is possible to more sufficiently solve this problem.

Moreover, if the treatment temperature is higher than 150° C., the catalytic action of the first N- and H-containing gas, which will be described later, is weakened, and the reaction for forming the oligomer-containing layer described above may be difficult to proceed. In this case, the detachment of the oligomer produced on the surface of the wafer 200 and in the recesses is more dominant than the growth, and it is difficult to form an oligomer-containing layer on the surface of the wafer 200 and in the recesses. can be This problem can be solved by setting the treatment temperature to 150° C. or lower. By setting the treatment temperature to 100° C. or lower, it is possible to sufficiently solve this problem, and by setting the treatment temperature to 60° C. or lower, it is possible to more sufficiently solve this problem.

For these reasons, the treatment temperature is desirably 0° C. or higher and 150° C. or lower, preferably 10° C. or higher and 100° C. or lower, more preferably 20° C. or higher and 60° C. or lower.

The processing conditions for purging are as follows.
Inert gas supply flow rate (each gas supply pipe): 10 to 20000 sccm
Inert gas supply time: 1 to 300 seconds Processing pressure: 10 to 6000 Pa
are exemplified. Other processing conditions can be the same as the processing conditions for supplying the raw material gas.

By purging under the above-described processing conditions, while promoting the flow of the oligomer-containing layer formed on the surface of the wafer 200 and in the concave portion, excess components contained in the oligomer-containing layer, such as excess gas and Cl. It is possible to discharge by-products containing

(post treatment)
After the oligomer-containing layer is formed on the surface of wafer 200 and in the recesses, the temperature of wafer 200 is changed to a second temperature greater than or equal to the first temperature described above, preferably lower than the first temperature described above. The output of heater 207 is adjusted so as to change to the higher second temperature.

At this time, an inert gas such as N ₂ gas is supplied as the N-containing gas to the wafer 200 in the processing chamber 201 . Specifically, the valves 243e to 243g are opened to flow the inert gas into the gas supply pipes 232e to 232g. The flow rate of the inert gas is adjusted by the MFCs 241e to 241g, supplied into the processing chamber 201 through the nozzles 249a to 249c, and exhausted from the exhaust port 231a. At this time, inert gas is supplied to the wafer 200 .

This step is preferably performed under conditions that make the oligomer-containing layer formed on the surface of the wafer 200 and in the recesses fluid. In addition, this step promotes the flow of the oligomer-containing layer formed on the surface of the wafer 200 and in the concave portion, while removing excess components contained in the oligomer-containing layer, such as excess gas and by-products including Cl. It is preferably carried out under conditions that allow for evacuation and densification of the oligomer-containing layer.

The processing conditions for post-treatment are as follows.
Inert gas supply flow rate (each gas supply pipe): 10 to 20000 sccm
Treatment temperature (second temperature): 100 to 1000°C, preferably 200 to 600°C
Treatment pressure: 10 to 80000 Pa, preferably 200 to 6000 Pa
Processing time: 300 to 10800 seconds are exemplified.

By performing the post treatment under the conditions described above, the oligomer-containing layer formed on the surface of the wafer 200 and in the recess can be modified. This makes it possible to form a silicon carbonitride film (SiCN film), which is a film containing Si, C and N, as a film obtained by modifying the oligomer-containing layer so as to fill the recess. In addition, while promoting the fluidization of the oligomer-containing layer, it is possible to discharge excess components contained in the oligomer-containing layer and densify the oligomer-containing layer.

(After-purge and return to atmospheric pressure)
After the formation of the SiCN film is completed, an inert gas as a purge gas is supplied into the processing chamber 201 from each of the nozzles 249a to 249c, and exhausted from the exhaust port 231a. As a result, the inside of the processing chamber 201 is purged, and gas remaining in the processing chamber 201 and reaction by-products are removed from the inside of the processing chamber 201 (afterpurge). After that, the atmosphere in the processing chamber 201 is replaced with an inert gas (inert gas replacement), and the pressure in the processing chamber 201 is returned to normal pressure (atmospheric pressure recovery).

(boat unload and wafer discharge)
After that, the seal cap 219 is lowered by the boat elevator 115, and the lower end of the manifold 209 is opened. Then, the processed wafer 200 is unloaded from the reaction tube 203 from the lower end of the manifold 209 while being supported by the boat 217 (boat unloading). After the boat is unloaded, the shutter 219s is moved and the lower end opening of the manifold 209 is sealed by the shutter 219s via the O-ring 220c (shutter closed). The processed wafers 200 are carried out of the reaction tube 203 and then taken out from the boat 217 (wafer discharge).

(3) Effects of this aspect According to this aspect, one or more of the following effects can be obtained.

(a) By forming the oligomer-containing layer at the first temperature and performing the post-treatment at a second temperature equal to or higher than the first temperature, it is possible to improve the embedding characteristics of the film formed in the recess. becomes. By performing the post-treatment at a second temperature higher than the first temperature, the above effects can be further enhanced.

(b) In the formation of the oligomer-containing layer, when the source gas is present alone, the cycle is performed a predetermined number of times under conditions in which physical adsorption of the source gas is dominant over chemisorption of the source gas. The fluidity of the oligomer-containing layer can be increased, and the embedding characteristics of the film formed in the recess can be improved.

(c) in the oligomer-containing layer formation, the cycle is run under conditions where, when the source gas is present alone, the physisorption of the source gas predominates over the thermal decomposition of the source gas and the chemisorption of the source gas; By repeating the treatment a predetermined number of times, it becomes possible to increase the fluidity of the oligomer-containing layer. As a result, it is possible to improve the embedding characteristics of the film formed in the recess.

(d) in the formation of the oligomer-containing layer, under conditions where the raw material gas is not thermally decomposed when the raw material gas is present alone, but the physical adsorption of the raw material gas is dominant over the chemisorption of the raw material gas; By performing the cycle a predetermined number of times, it becomes possible to increase the fluidity of the oligomer-containing layer. As a result, it is possible to improve the embedding characteristics of the film formed in the recess.

(e) In the formation of the oligomer-containing layer, it is possible to improve the embedding characteristics of the film formed in the recess by repeating the cycle a predetermined number of times under conditions that make the oligomer-containing layer fluid.

(f) In the formation of the oligomer-containing layer, the oligomer-containing layer is caused to flow into the depth of the recess, and the recess is filled with the oligomer-containing layer from the depth of the recess. It is possible to improve the embedding characteristics of the film formed inside.

(g) By using an alkylchlorosilane-based gas as a raw material gas, it is possible to make the oligomer-containing layer contain Si, C, and Cl.

(h) By differentiating the molecular structure of the first N- and H-containing gas from the molecular structure of the second N- and H-containing gas, each gas can play a different role. For example, as in the present embodiment, by using an amine-based gas as the first N- and H-containing gas, this gas acts as a catalyst to activate the raw material gas physically adsorbed on the surface of the wafer 200 by supplying the raw material gas. becomes possible. Further, by using a hydrogen nitride-based gas as the second N- and H-containing gas, this gas can be made to act as an N source, and N can be included in the oligomer-containing layer.

(i) In the formation of the oligomer-containing layer, a cycle of non-simultaneously supplying the raw material gas, supplying the first N- and H-containing gas, and supplying the second N- and H-containing gas is performed a predetermined number of times to form the layer in the recess. It is possible to improve the embedding characteristics of the film.

In this method, the raw material gas and the first N- and H-containing gas acting as a catalyst are supplied separately at different timings to control variations in the degree of mixing between the raw material gas and the first N- and H-containing gas. It is thought that this is due to the fact that According to this aspect, the variation in the growth of each oligomer generated in a plurality of places on the surface of the wafer 200 and in the recess is improved, the variation in growth in a fine region is suppressed, and the resulting voids and the like in the recess. It is possible to suppress the occurrence of seams and the like. As a result, it is possible to improve the embedding characteristics of the film formed in the recess. That is, void-free and seamless embedding becomes possible.

(j) In the formation of the oligomer-containing layer, by performing purging at a predetermined timing, it is possible to improve the embedding characteristics of the film formed in the concave portion. Further, it is possible to reduce the impurity concentration of the film formed so as to fill the recess. This makes it possible to improve the wet etching resistance of the film formed in the recess.

(k) By performing the post-treatment under conditions that make the oligomer-containing layer fluid, it is possible to improve the embedding characteristics of the film formed in the concave portion.

(l) In the post treatment, while promoting the fluidization of the oligomer-containing layer, surplus components contained in the oligomer-containing layer are discharged and the oligomer-containing layer is densified, thereby improving the embedding characteristics of the film formed in the recess. can be improved. In addition, it is possible to reduce the impurity concentration of the film formed so as to fill the recess, and further to increase the film density. As a result, the wet etching resistance of the film formed in the recess can be improved.

(m) By supplying N-containing gas to the wafer 200 in post-treatment, it is possible to promote the flow of the oligomer-containing layer and improve the embedding characteristics of the film formed in the concave portion. In addition, it is possible to reduce the impurity concentration of the film formed so as to fill the recess, and further to increase the film density. As a result, the wet etching resistance of the film formed in the recess can be improved.

(n) The above effect is obtained when the above various raw material gases, the above various first N- and H-containing gases, the above-mentioned various second N- and H-containing gases, and the above-mentioned various inert gases are used in forming the oligomer-containing layer. can be similarly obtained. Moreover, the above effects can be similarly obtained even when the order of gas supply in the cycle is changed. Moreover, the above-mentioned effect can be similarly obtained even when using a gas other than the N-containing gas in the post treatment.

<Second aspect of the present disclosure>
Next, the second aspect of the present disclosure will be described mainly with reference to FIG.

As in FIG. 5 and the processing sequence shown below, oligomer-containing layer formation involves:
simultaneously performing a step of supplying a source gas to the wafer 200 and a step of supplying a first N- and H-containing gas to the wafer 200;
supplying a second N and H containing gas to the wafer 200;
may be performed a predetermined number of times (n times, where n is an integer equal to or greater than 1).

(source gas + first N- and H-containing gas → second N- and H-containing gas) × n → PT

This aspect also provides the same effects as the above-described first aspect. Moreover, in this aspect, since the raw material gas and the first N- and H-containing gas are simultaneously supplied, it is possible to improve the cycle rate and increase the productivity of substrate processing.

<Third aspect of the present disclosure>
Next, the third aspect of the present disclosure will be described mainly with reference to FIG.

As in FIG. 6 and the processing sequence shown below, in forming the oligomer-containing layer,
simultaneously performing a step of supplying a source gas to the wafer 200 and a step of supplying a first N- and H-containing gas to the wafer 200;
supplying a second N and H containing gas to the wafer 200;
supplying a first N and H containing gas to the wafer 200;
may be performed a predetermined number of times (n times, where n is an integer equal to or greater than 1).

(source gas + first N- and H-containing gas → second N- and H-containing gas → first N- and H-containing gas) × n → PT

This aspect also provides the same effects as the above-described first aspect. In addition, in this aspect, the first N- and H-containing gas that is flowed for the first time in the cycle can act as a catalyst to activate the raw material gas. In addition, the first N- and H-containing gas, which is flowed for the second time during the cycle, can be made to act as a gas for removing by-products generated during the formation of the oligomer-containing layer, that is, as a reactive purge gas. The processing conditions for supplying these first N- and H-containing gases can be the same as the processing conditions for supplying the above-described first N- and H-containing gases.

<Other aspects of the present disclosure>
Various aspects of the present disclosure have been specifically described above. However, the present disclosure is not limited to the embodiments described above, and various modifications can be made without departing from the scope of the present disclosure.

For example, in the post treatment, an H-containing gas such as hydrogen (H ₂ ) gas may be supplied to the wafer 200 on which the oligomer-containing layer is formed, and an N-containing gas such as NH ₃ gas, namely N and H A containing gas may be supplied, and an O-containing gas such as H ₂ O gas, that is, an O- and H-containing gas may be supplied. Note that O ₂ gas may be supplied as the O-containing gas. That is, in the post treatment, at least one of N-containing gas, H-containing gas, N- and H-containing gas, O-containing gas, and O- and H-containing gas is supplied to the wafer 200 on which the oligomer-containing layer is formed. may

The processing conditions for supplying the H-containing gas in post-treatment are as follows:
H-containing gas supply flow rate: 10 to 3000 sccm
Treatment temperature (second temperature): 100 to 1000°C, preferably 200 to 600°C
Treatment pressure: 10-1000 Pa, preferably 200-800 Pa
Processing time: 300 to 10800 seconds are exemplified.

The processing conditions for supplying the N- and H-containing gas in post-treatment are as follows:
N and H containing gas supply flow rate: 10 to 10000 sccm
Treatment temperature (second temperature): 100 to 1000°C, preferably 200 to 600°C
Treatment pressure: 10-6000 Pa, preferably 200-2000 Pa
Processing time: 300 to 10800 seconds are exemplified.

The processing conditions for supplying the O-containing gas in post-treatment are as follows:
O-containing gas supply flow rate: 10 to 10000 sccm
Treatment temperature (second temperature): 100 to 1000°C, preferably 100 to 600°C
Treatment pressure: 10 to 90000 Pa, preferably 20000 to 80000 Pa
Processing time: 300 to 10800 seconds are exemplified.

Even in these cases, the same effects as in the above-described first mode can be obtained.

It should be noted that post-treatment in an H-containing gas atmosphere or N- and H-containing gas atmosphere is more effective than post-treatment in an inert gas atmosphere such as _N2 gas. , it is possible to increase the fluidity of the oligomer-containing layer and improve the embedding characteristics of the film formed in the recess. In addition, when post-treatment is performed in an H-containing gas atmosphere or in an N- and H-containing gas atmosphere, post-treatment is performed in an inert gas atmosphere such as _N2 gas. , the impurity concentration of the film formed in the recess can be reduced, the film density can be increased, and the wet etching resistance can be improved. These effects can be enhanced when post-treatment is performed in an N- and H-containing gas atmosphere as compared to when post-treatment is performed in an H-containing gas atmosphere.

Note that when post-treatment is performed in an O-containing gas atmosphere, O can be included in the film obtained by modifying the oligomer-containing layer. A silicon oxynitride carbide film (SiOCN film) can be obtained.

For example, in post-treatment,
At least one of N-containing gas such as _N2 gas, H-containing gas such as _H2 gas, and N and H-containing gas such as _NH3 gas is supplied to the wafer 200 on which the oligomer-containing layer is formed. a step;
supplying an O-containing gas (O- and H-containing gas) such as H ₂ O gas to the wafer 200 on which the oligomer-containing layer is formed;
may be performed non-simultaneously. In this case, of the two steps, the former step can be called the first post-treatment, and the latter step can be called the second post-treatment.

The processing conditions in each of the first and second post-treatments can be the same as the processing conditions in the post-treatments of the above embodiments.

Even in this case, the same effect as in the above-described first mode can be obtained.

Note that when the post-treatment is performed in an O-containing gas atmosphere, O can be included in the film obtained by modifying the oligomer-containing layer, and this film can be made into a SiOCN film. In addition, by using an O- and H-containing gas such as H ₂ O gas with relatively low oxidizing power as the O-containing gas, desorption of C from the SiOCN film formed by modifying the oligomer-containing layer can be suppressed. becomes possible. Further, by performing the first and second post treatments in this order, it is possible to suppress desorption of C from the SiOCN film obtained by modifying the oligomer-containing layer.

Further, for example, the first mode and part of the third mode may be combined as in the processing sequence shown below.

(source gas → first N- and H-containing gas → second N- and H-containing gas → first N- and H-containing gas) × n → PT

That is, in oligomer-containing layer formation,
supplying a raw material gas to the wafer 200;
supplying a first N and H containing gas to the wafer 200;
supplying a second N and H containing gas to the wafer 200;
supplying a first N and H containing gas to the wafer 200;
may be performed a predetermined number of times (n times, where n is an integer equal to or greater than 1).

According to this processing sequence, it is possible to obtain both the effect obtained by the first aspect and the effect obtained by part of the third aspect.

In the above embodiment, the example in which the formation of the oligomer-containing layer and the post-treatment are performed in the same processing chamber 201 (in-situ) has been described. However, the present disclosure is not limited to such aspects. For example, oligomer-containing layer formation and post-treatment may be performed in separate processing chambers (ex-situ). Even in this case, the same effect as that in the above-described mode can be obtained. In the various cases described above, if these steps are performed in-situ, the wafer 200 is not exposed to the atmosphere during the process, and these processes can be performed consistently while the wafer 200 is under vacuum. It is possible to perform stable substrate processing. In addition, if these steps are performed ex-situ, the temperature in each processing chamber can be set in advance to, for example, the processing temperature in each step or a temperature close thereto, shortening the time required for temperature adjustment, Production efficiency can be improved.

So far, an example of forming the SiCN film or the SiOCN film so as to fill the concave portion formed on the surface of the wafer 200 has been described, but the present disclosure is not limited to these examples. That is, by arbitrarily combining the source gas, the first N- and H-containing gas, and the second N- and H-containing gas, a silicon nitride film (SiN film), silicon The present disclosure can also be suitably applied when forming an oxide film (SiO film), a silicon oxycarbide film (SiOC film), or a silicon film (Si film). Also in these cases, the same effects as those in the above-described embodiments can be obtained.

Recipes used for substrate processing are preferably prepared individually according to the processing contents and stored in the storage device 121c via an electric communication line or the external storage device 123 . Then, when starting the processing, it is preferable that the CPU 121a appropriately selects an appropriate recipe from among the plurality of recipes stored in the storage device 121c according to the content of the substrate processing. As a result, a single substrate processing apparatus can form films having various film types, composition ratios, film qualities, and film thicknesses with good reproducibility. In addition, the burden on the operator can be reduced, and the processing can be started quickly while avoiding operational errors.

The above-described recipe is not limited to the case of newly creating the recipe, but may be prepared by modifying an existing recipe that has already been installed in the substrate processing apparatus, for example. When changing the recipe, the changed recipe may be installed in the substrate processing apparatus via an electric communication line or a recording medium recording the recipe. Alternatively, an existing recipe already installed in the substrate processing apparatus may be directly changed by operating the input/output device 122 provided in the existing substrate processing apparatus.

In the above embodiment, an example of forming a film using a batch-type substrate processing apparatus that processes a plurality of substrates at once has been described. The present disclosure is not limited to the embodiments described above, and can be suitably applied, for example, to the case of forming a film using a single substrate processing apparatus that processes one or several substrates at a time. Further, in the above embodiments, an example of forming a film using a substrate processing apparatus having a hot wall type processing furnace has been described. The present disclosure is not limited to the above embodiments, and can be suitably applied to the case of forming a film using a substrate processing apparatus having a cold wall type processing furnace.

Even when these substrate processing apparatuses are used, film formation can be performed under the same sequence and processing conditions as in the above embodiments and modifications, and the same effects as these can be obtained.

In addition, the above aspects, modifications, and the like can be used in combination as appropriate. The processing procedure and processing conditions at this time can be, for example, the same as the processing procedures and processing conditions of the above-described mode.

200 wafer (substrate)
201 processing chamber

Claims (28)

(a) simultaneously performing a step of supplying a source gas to a substrate having recesses formed on its surface and a step of supplying a first nitrogen- and hydrogen-containing gas to the substrate;
supplying a second nitrogen and hydrogen containing gas to the substrate;
at a first temperature for a predetermined number of times to produce an oligomer containing an element contained in at least one of the raw material gas, the first nitrogen- and hydrogen-containing gas, and the second nitrogen- and hydrogen-containing gas on the surface of the substrate and in the recesses, growing and flowing to form an oligomer-containing layer on the surface of the substrate and in the recesses;
(b) performing post-treatment at a second temperature equal to or higher than the first temperature on the substrate having the oligomer-containing layer formed on the surface of the substrate and in the concave portion, thereby modifying the oligomer-containing layer formed in the recess to form a film obtained by modifying the oligomer-containing layer so as to fill the recess;
A substrate processing method comprising: (a) simultaneously performing a step of supplying a source gas to a substrate having recesses formed on its surface and a step of supplying a first nitrogen- and hydrogen-containing gas to the substrate;
supplying a second nitrogen and hydrogen containing gas to the substrate;
supplying the first nitrogen- and hydrogen-containing gas to the substrate;
at a first temperature for a predetermined number of times to produce an oligomer containing an element contained in at least one of the raw material gas, the first nitrogen- and hydrogen-containing gas, and the second nitrogen- and hydrogen-containing gas on the surface of the substrate and in the recesses, growing and flowing to form an oligomer-containing layer on the surface of the substrate and in the recesses;
(b) performing post-treatment at a second temperature equal to or higher than the first temperature on the substrate having the oligomer-containing layer formed on the surface of the substrate and in the concave portion, thereby modifying the oligomer-containing layer formed in the recess to form a film obtained by modifying the oligomer-containing layer so as to fill the recess;
A substrate processing method comprising : (a) supplying a raw material gas containing silicon and halogen to a substrate having recesses formed on its surface ; supplying a first nitrogen- and hydrogen-containing gas to the substrate; and supplying a second nitrogen- and hydrogen-containing gas at a first temperature for a predetermined number of times to obtain the raw material gas, the first nitrogen- and hydrogen-containing gas, and the second nitrogen and hydrogen An oligomer containing an element contained in at least one of the contained gases is generated on the surface of the substrate and in the recess, grown, and flowed to form an oligomer-containing layer on the surface of the substrate and in the recess. forming;
(b) performing post-treatment at a second temperature equal to or higher than the first temperature on the substrate having the oligomer-containing layer formed on the surface of the substrate and in the concave portion, thereby modifying the oligomer-containing layer formed in the recess to form a film obtained by modifying the oligomer-containing layer so as to fill the recess;
A substrate processing method comprising : (a) supplying a source gas to a substrate having recesses formed on its surface; supplying a first nitrogen- and hydrogen-containing gas to the substrate; and supplying a second nitrogen- and hydrogen-containing gas to the substrate; and supplying the containing gas at a first temperature for a predetermined number of times, at least any one of the source gas, the first nitrogen- and hydrogen-containing gas, and the second nitrogen- and hydrogen-containing gas a step of forming an oligomer containing an element on the surface of the substrate and in the recess, allowing it to grow and flow to form an oligomer-containing layer on the surface of the substrate and in the recess;
(b) performing post-treatment at a second temperature equal to or higher than the first temperature on the substrate having the oligomer-containing layer formed on the surface of the substrate and in the concave portion, thereby modifying the oligomer-containing layer formed in the recess to form a film obtained by modifying the oligomer-containing layer so as to fill the recess;
has
(b) is
supplying at least one of a nitrogen-containing gas, a hydrogen-containing gas, and a nitrogen and hydrogen-containing gas to the substrate;
supplying an oxygen-containing gas to the substrate;
A substrate processing method comprising: In (a), when the source gas exists alone, the cycle is performed a predetermined number of times under conditions in which the physical adsorption of the source gas is dominant over the chemisorption of the source gas. 5. The substrate processing method according to any one of items 1 to 4 . In (a), when the raw material gas exists alone,
or
Under conditions in which physical adsorption of the raw material gas is dominant over chemisorption of the raw material gas without thermal decomposition of the raw material gas,
6. The substrate processing method according to claim 1, wherein said cycle is performed a predetermined number of times. 7. The substrate processing method according to any one of claims 1 to 6, wherein in (a), the cycle is performed a predetermined number of times under conditions that make the oligomer-containing layer fluid. In (a), the cycle is performed a predetermined number of times under the condition that the oligomer-containing layer is allowed to flow deep into the recess, and the oligomer-containing layer fills the recess from the deep inside of the recess. 8. The substrate processing method according to any one of 1 to 7 . The cycle in (a) comprises:
supplying the raw material gas to the substrate;
supplying the first nitrogen- and hydrogen-containing gas to the substrate;
supplying the second nitrogen- and hydrogen-containing gas to the substrate;
5. The substrate processing method according to claim 3 or 4, comprising performing non-simultaneously. The cycle in (a) further includes purging the space in which the substrate resides;
The substrate processing method according to any one of claims 1 to 9, wherein the purging promotes fluidization of the oligomer-containing layer and discharges surplus components contained in the oligomer-containing layer. 11. The substrate processing method according to any one of claims 1 to 10, wherein in (b), the post-treatment is performed under conditions that make the oligomer-containing layer fluid. 12. The method according to any one of claims 1 to 11, wherein in (b), excess components contained in the oligomer-containing layer are discharged while promoting fluidization of the oligomer-containing layer to densify the oligomer-containing layer. Substrate processing method. 13. The substrate processing method according to claim 1, wherein the raw material gas contains silicon, carbon, and halogen. The substrate processing method according to any one of claims 1 to 13, wherein the first nitrogen- and hydrogen-containing gas and the second nitrogen- and hydrogen-containing gas have different molecular structures. The substrate processing method according to any one of claims 1 to 14 , wherein the first nitrogen- and hydrogen-containing gas is an amine-based gas, and the second nitrogen- and hydrogen-containing gas is a hydrogen nitride-based gas. 16. The method according to any one of claims 1 to 15, wherein in (b), at least one of a nitrogen-containing gas, a hydrogen-containing gas, a nitrogen and hydrogen-containing gas, and an oxygen-containing gas is supplied to the substrate. Substrate processing method. (a) simultaneously performing a step of supplying a source gas to a substrate having recesses formed on its surface and a step of supplying a first nitrogen- and hydrogen-containing gas to the substrate;
supplying a second nitrogen and hydrogen containing gas to the substrate;
at a first temperature for a predetermined number of times to produce an oligomer containing an element contained in at least one of the raw material gas, the first nitrogen- and hydrogen-containing gas, and the second nitrogen- and hydrogen-containing gas on the surface of the substrate and in the recesses, growing and flowing to form an oligomer-containing layer on the surface of the substrate and in the recesses;
(b) performing post-treatment at a second temperature equal to or higher than the first temperature on the substrate having the oligomer-containing layer formed on the surface of the substrate and in the concave portion, thereby modifying the oligomer-containing layer formed in the recess to form a film obtained by modifying the oligomer-containing layer so as to fill the recess;
A method of manufacturing a semiconductor device having (a) simultaneously performing a step of supplying a source gas to a substrate having recesses formed on its surface and a step of supplying a first nitrogen- and hydrogen-containing gas to the substrate;
supplying a second nitrogen and hydrogen containing gas to the substrate;
supplying the first nitrogen- and hydrogen-containing gas to the substrate;
at a first temperature for a predetermined number of times to produce an oligomer containing an element contained in at least one of the raw material gas, the first nitrogen- and hydrogen-containing gas, and the second nitrogen- and hydrogen-containing gas on the surface of the substrate and in the recesses, growing and flowing to form an oligomer-containing layer on the surface of the substrate and in the recesses;
(b) performing post-treatment at a second temperature equal to or higher than the first temperature on the substrate having the oligomer-containing layer formed on the surface of the substrate and in the concave portion, thereby modifying the oligomer-containing layer formed in the recess to form a film obtained by modifying the oligomer-containing layer so as to fill the recess;
A method of manufacturing a semiconductor device having (a) supplying a raw material gas containing silicon and halogen to a substrate having recesses formed on its surface; supplying a first nitrogen- and hydrogen-containing gas to the substrate; and supplying a second nitrogen- and hydrogen-containing gas at a first temperature for a predetermined number of times to obtain the raw material gas, the first nitrogen- and hydrogen-containing gas, and the second nitrogen and hydrogen An oligomer containing an element contained in at least one of the contained gases is generated on the surface of the substrate and in the recess, grown, and flowed to form an oligomer-containing layer on the surface of the substrate and in the recess. forming;
(b) performing post-treatment at a second temperature equal to or higher than the first temperature on the substrate having the oligomer-containing layer formed on the surface of the substrate and in the concave portion, thereby modifying the oligomer-containing layer formed in the recess to form a film obtained by modifying the oligomer-containing layer so as to fill the recess;
A method of manufacturing a semiconductor device having (a) supplying a source gas to a substrate having recesses formed on its surface; supplying a first nitrogen- and hydrogen-containing gas to the substrate; and supplying a second nitrogen- and hydrogen-containing gas to the substrate; and supplying the containing gas at a first temperature for a predetermined number of times, at least any one of the source gas, the first nitrogen- and hydrogen-containing gas, and the second nitrogen- and hydrogen-containing gas a step of forming an oligomer containing an element on the surface of the substrate and in the recess, allowing it to grow and flow to form an oligomer-containing layer on the surface of the substrate and in the recess;
(b) performing post-treatment at a second temperature equal to or higher than the first temperature on the substrate having the oligomer-containing layer formed on the surface of the substrate and in the concave portion, thereby modifying the oligomer-containing layer formed in the recess to form a film obtained by modifying the oligomer-containing layer so as to fill the recess;
has
(b) is
supplying at least one of a nitrogen-containing gas, a hydrogen-containing gas, and a nitrogen and hydrogen-containing gas to the substrate;
supplying an oxygen-containing gas to the substrate;
A method of manufacturing a semiconductor device comprising: a raw material gas supply system for supplying a raw material gas to the substrate ;
a first nitrogen- and hydrogen-containing gas supply system for supplying a first nitrogen- and hydrogen-containing gas to the substrate ;
a second nitrogen- and hydrogen-containing gas supply system for supplying a second nitrogen- and hydrogen-containing gas to the substrate ;
a heater for heating the substrate ;
( a) a process of simultaneously performing a process of supplying the raw material gas to a substrate having recesses formed on its surface and a process of supplying the first nitrogen- and hydrogen-containing gas to the substrate;
supplying the second nitrogen- and hydrogen-containing gas to the substrate;
at a first temperature for a predetermined number of times to produce an oligomer containing an element contained in at least one of the raw material gas, the first nitrogen- and hydrogen-containing gas, and the second nitrogen- and hydrogen-containing gas on the surface of the substrate and in the recesses, grow and flow to form an oligomer-containing layer on the surface of the substrate and in the recesses;
(b) performing post-treatment at a second temperature equal to or higher than the first temperature on the substrate in which the oligomer-containing layer is formed on the surface of the substrate and in the recess, thereby removing the a process of modifying the oligomer-containing layer formed in the recess to form a film in which the oligomer-containing layer is modified so as to fill the recess;
A control unit configured to be able to control the source gas supply system, the first nitrogen- and hydrogen-containing gas supply system, the second nitrogen- and hydrogen-containing gas supply system, and the heater so as to perform and,
A substrate processing apparatus having a raw material gas supply system for supplying a raw material gas to the substrate;
a first nitrogen- and hydrogen-containing gas supply system for supplying a first nitrogen- and hydrogen-containing gas to the substrate;
a second nitrogen- and hydrogen-containing gas supply system for supplying a second nitrogen- and hydrogen-containing gas to the substrate;
a heater for heating the substrate;
(a) a process of simultaneously performing a process of supplying the source gas to a substrate having recesses formed on its surface and a process of supplying the first nitrogen- and hydrogen-containing gas to the substrate;
supplying the second nitrogen- and hydrogen-containing gas to the substrate;
supplying the first nitrogen- and hydrogen-containing gas to the substrate;
at a first temperature for a predetermined number of times to produce an oligomer containing an element contained in at least one of the raw material gas, the first nitrogen- and hydrogen-containing gas, and the second nitrogen- and hydrogen-containing gas on the surface of the substrate and in the recesses, grow and flow to form an oligomer-containing layer on the surface of the substrate and in the recesses;
(b) performing post-treatment at a second temperature equal to or higher than the first temperature on the substrate in which the oligomer-containing layer is formed on the surface of the substrate and in the recess, thereby removing the a process of modifying the oligomer-containing layer formed in the recess to form a film in which the oligomer-containing layer is modified so as to fill the recess;
A control unit configured to be able to control the source gas supply system, the first nitrogen- and hydrogen-containing gas supply system, the second nitrogen- and hydrogen-containing gas supply system, and the heater so as to perform and,
A substrate processing apparatus having a raw material gas supply system for supplying a raw material gas containing silicon and halogen to a substrate;
a first nitrogen- and hydrogen-containing gas supply system for supplying a first nitrogen- and hydrogen-containing gas to the substrate;
a second nitrogen- and hydrogen-containing gas supply system for supplying a second nitrogen- and hydrogen-containing gas to the substrate;
a heater for heating the substrate;
(a) a process of supplying the source gas to a substrate having recesses formed on its surface; a process of supplying the first nitrogen- and hydrogen-containing gas to the substrate; supplying a nitrogen- and hydrogen-containing gas, and performing a cycle at a first temperature for a predetermined number of times to obtain the raw material gas, the first nitrogen- and hydrogen-containing gas, and the second nitrogen- and hydrogen-containing gas. A process of forming an oligomer containing an element contained in at least one of the elements on the surface of the substrate and in the recess, growing and flowing to form an oligomer-containing layer on the surface of the substrate and in the recess. and,
(b) performing post-treatment at a second temperature equal to or higher than the first temperature on the substrate in which the oligomer-containing layer is formed on the surface of the substrate and in the recess, thereby removing the a process of modifying the oligomer-containing layer formed in the recess to form a film in which the oligomer-containing layer is modified so as to fill the recess;
A control unit configured to be able to control the source gas supply system, the first nitrogen- and hydrogen-containing gas supply system, the second nitrogen- and hydrogen-containing gas supply system, and the heater so as to perform and,
A substrate processing apparatus having a raw material gas supply system for supplying a raw material gas to the substrate;
a first nitrogen- and hydrogen-containing gas supply system for supplying a first nitrogen- and hydrogen-containing gas to the substrate;
a second nitrogen- and hydrogen-containing gas supply system for supplying a second nitrogen- and hydrogen-containing gas to the substrate;
a nitrogen- and/or hydrogen-containing gas supply system that supplies at least one of a nitrogen-containing gas, a hydrogen-containing gas, and a nitrogen- and hydrogen-containing gas to the substrate;
an oxygen-containing gas supply system that supplies an oxygen-containing gas to the substrate;
a heater for heating the substrate;
(a) a process of supplying the source gas to a substrate having recesses formed on its surface; a process of supplying the first nitrogen- and hydrogen-containing gas to the substrate; supplying a nitrogen- and hydrogen-containing gas, and performing a cycle at a first temperature for a predetermined number of times to obtain the raw material gas, the first nitrogen- and hydrogen-containing gas, and the second nitrogen- and hydrogen-containing gas. A process of forming an oligomer containing an element contained in at least one of the elements on the surface of the substrate and in the recess, growing and flowing to form an oligomer-containing layer on the surface of the substrate and in the recess. and,
(b) performing post-treatment at a second temperature equal to or higher than the first temperature on the substrate in which the oligomer-containing layer is formed on the surface of the substrate and in the recess, thereby removing the a process of modifying the oligomer-containing layer formed in the recess to form a film in which the oligomer-containing layer is modified so as to fill the recess;
in (b)
a process of supplying at least one of the nitrogen-containing gas, the hydrogen-containing gas, and the nitrogen and hydrogen-containing gas to the substrate;
a process of supplying the oxygen-containing gas to the substrate;
the source gas supply system, the first nitrogen- and hydrogen-containing gas supply system, the second nitrogen- and hydrogen-containing gas supply system, the nitrogen and/or hydrogen-containing gas supply system, and the oxygen-containing gas supply system a control unit configured to be able to control a system and the heater;
A substrate processing apparatus having (a) simultaneously performing a step of supplying a raw material gas to a substrate having recesses formed on its surface and a step of supplying a first nitrogen- and hydrogen-containing gas to the substrate;
supplying a second nitrogen and hydrogen containing gas to the substrate;
at a first temperature for a predetermined number of times to produce an oligomer containing an element contained in at least one of the raw material gas, the first nitrogen- and hydrogen-containing gas, and the second nitrogen- and hydrogen-containing gas on the surface of the substrate and in the recesses, growing and flowing to form an oligomer-containing layer on the surface of the substrate and in the recesses;
(b) performing post-treatment at a second temperature equal to or higher than the first temperature on the substrate having the oligomer-containing layer formed on the surface of the substrate and in the concave portion, thereby a step of modifying the oligomer-containing layer formed in the recess to form a film in which the oligomer-containing layer is modified so as to fill the recess;
A program that causes a substrate processing apparatus to execute by a computer. (a) simultaneously performing a step of supplying a raw material gas to a substrate having recesses formed on its surface and a step of supplying a first nitrogen- and hydrogen-containing gas to the substrate;
supplying a second nitrogen and hydrogen containing gas to the substrate;
supplying the first nitrogen and hydrogen containing gas to the substrate;
at a first temperature for a predetermined number of times to produce an oligomer containing an element contained in at least one of the raw material gas, the first nitrogen- and hydrogen-containing gas, and the second nitrogen- and hydrogen-containing gas on the surface of the substrate and in the recesses, growing and flowing to form an oligomer-containing layer on the surface of the substrate and in the recesses;
(b) performing post-treatment at a second temperature equal to or higher than the first temperature on the substrate having the oligomer-containing layer formed on the surface of the substrate and in the concave portion, thereby a step of modifying the oligomer-containing layer formed in the recess to form a film in which the oligomer-containing layer is modified so as to fill the recess;
A program that causes a substrate processing apparatus to execute by a computer. (a) a step of supplying a raw material gas containing silicon and halogen to a substrate having recesses formed on its surface; a step of supplying a first nitrogen- and hydrogen-containing gas to the substrate; and supplying a second nitrogen- and hydrogen-containing gas at a first temperature for a predetermined number of times to obtain the source gas, the first nitrogen- and hydrogen-containing gas, and the second nitrogen and hydrogen An oligomer containing an element contained in at least one of the contained gases is generated on the surface of the substrate and in the recess, grown, and flowed to form an oligomer-containing layer on the surface of the substrate and in the recess. a forming procedure;
(b) performing post-treatment at a second temperature equal to or higher than the first temperature on the substrate having the oligomer-containing layer formed on the surface of the substrate and in the concave portion, thereby a step of modifying the oligomer-containing layer formed in the recess to form a film in which the oligomer-containing layer is modified so as to fill the recess;
A program that causes a substrate processing apparatus to execute by a computer. (a) a step of supplying a source gas to a substrate having recesses formed on its surface, a step of supplying a first nitrogen- and hydrogen-containing gas to the substrate, and a step of supplying a second nitrogen- and hydrogen-containing gas to the substrate; and supplying the containing gas at a first temperature for a predetermined number of times, at least any one of the source gas, the first nitrogen- and hydrogen-containing gas, and the second nitrogen- and hydrogen-containing gas a step of forming an oligomer containing an element contained in the above on the surface of the substrate and in the recess, growing and flowing to form an oligomer-containing layer on the surface of the substrate and in the recess;
(b) performing post-treatment at a second temperature equal to or higher than the first temperature on the substrate having the oligomer-containing layer formed on the surface of the substrate and in the concave portion, thereby a step of modifying the oligomer-containing layer formed in the recess to form a film in which the oligomer-containing layer is modified so as to fill the recess;
in (b)
supplying at least one of a nitrogen-containing gas, a hydrogen-containing gas, and a nitrogen and hydrogen-containing gas to the substrate;
supplying an oxygen-containing gas to the substrate;
A program that causes a substrate processing apparatus to execute by a computer.

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